Method of treating mineral oil products and product thereof



Patented Aug. 6, 1935 UNITED STATES METHOD OF TREATING MINERAL OIL PRODUCTS AND PRODUCT THEREOF Joseph Hidy James, Pittsburgh, Pa... assignor to Clarence No Drawing.

8 Claims.

This application is a continuation in part of my co-pending application, Serial No. 473,798, filed May 31, 1921, and relates particularly to the partial oxidation of products derived from the cracking of mineral oil hydrocarbons or their derivatives.

In several co-pending applications, including Serial Nos. 272,567, filed January 22, 1919; 281,124, filed March 7, 1919, and 335,939, filed Nov. 5, 1919 which has matured into Patent No. 1,759,620, I have described a process for making intermediate or partial oxidation products from mineralhydrocarbons, such as petroleum, petroleum distillates, shale oil and its distillates, and so forth. These applications mainly relate to making products themolecules of which have. as nearly as possible, the same number of carbon atoms as the hydrocarbons used as raw material. The present invention is designed to prepare mixtures of oxidation products and hydrocarbons the molecules of which have fewer atoms than the hydrocarbonsof the raw material. The process followed out is generally the same as in the said applications, namely, vaporizing the hydrocarbon the same as a liquid, mixing it with air or an oxygen containing gas, and in some cases diluent, such as steam, and passing the vapor or gaseous phase mixture through a catalytic layer at a temperature between certain defined limits and below that of continuous self-sustained combustion. This temperature is preferably also below a red heat and within the range where partial oxidation products are produced.

Under the present invention I prefer to use higher temperature conditions than in former types of my process, where the main products were for other than fuel u'ses, By using a somewhat higher temperature and a higher ratio of air, I not only effect a partial oxidation of the hydrocarbons treated, but in part, dec0mposi tion of the oxidation products at the higher temperature, this giving a higher percentage of carbon monoxide and carbon dioxide in the offtake gases and producing hydrocarbons of lower carbon content than those of the mixture charged. This thermal decomposition takes place to some extent in my process for making other products, but is increased by the higher temperature and higher air ratio. This thermal decomposition of the oxidation products also results in the formation of oxygen derivatives of lower carbon content than the original hydrocarbons.

The temperature employed may extend from 230 C. up to over 400 C., and preferably is in P. Byrnes, trustee, Sewickley, Pa.

Application October 28, 1925, Serial No. 65,378

the upper part of this range, the air ratio being well beyond the theoretical proportions.

When the process is carried out in this manner, I find that a large proportion of the mixture consists of fuels, preferably for internal combustion engines, a considerable amount being within the gasoline or motor spirit range, while a larger proportion is within the kerosene range. I preferably fractionally distil the product, taking off, first, the gasoline or motor spirit fraction at its usual end point, and then at ahigher temperature, take off the kerosene product up to its usualend point. The remainder of the product may then be treated for producing lubricants or other industrial products. The motor spirit range at the present time extends to about 225" C. while the kerosene range extends from this point to up to around 300 C.

The liquid fuels thus produced are of bciier burning quality and more easily ignited than the ordinary hydrocarbon fractions within these ranges of distillation, owing to the greater content of oxygen, due to the oxidation process. The motor spirit produced may be employed in all ordinary internal combustion engines and the kerosene product may be employed in many types of internal combustion engines, such as those for tractor use, etc.

The fraction within the ordinary kerosene range may, if desired, be subjected to a second decomposition step of the usual cracking type. This cracking may be carried out in the liquid phase at temperatures giving from to 300 pounds per square inch pressure, or in the pressure liquid and vapor phase or in the pressure vapor phase. Or the mixture may be cracked by high frequency, high voltage electrical oscillations in the vapor phase or liquid phase or in the combined liquid and vapor phase.

As an example of one type of my process, I employ a fraction of Mexican fuel oil boiling from 300 C. to 360 C. This fraction was subjected to my partial oxidation process in the three screen apparatus of my British Patent No. 173,750, using as a catalyst the blue oxides of molybdenum deposited on asbestos for the catalytic layer. The temperature of vaporizer being about 330 Ci, an amount of water equal to about ten percent of the oil volume was fed with the oil to aid in vaporization. The air used was 1.5 liters per minute for every 100 cubic centimeters of oil fed per hour. The oil was fed at the rate of six liters per hour-and the air was distributed to the three screens, as noted in the above application. The temperature of the three catalytic screens varied om 380 C. to 400 C., during the run, which lasted for three hours.

The condensed, oxidized product was, in volume, equal to about% of the oil fed. This product contained about 30% by volume of aldehyde fatty acids and 20% by volume of aldehydes and aldehyde alcohols, the remaining 50% being made up of other oxygenated bodies, together with {hydrocarbons of low molecular weight, resulting from decomposition of oxygenated bo'dies.,

On distillation, the product gave 12% of a fraction boiling under 200' C. and 65% of a fraction boiling under 300 C. The'oxygenated bodies are If a heavy Mexican distillate is used or wax distillate from the mid-continental oils or gas oil or other by-products from the Pennsylvania or other ils, or pressure tar" a byproduct from the crack ng of oils) I prefer to distil the oxidized product taking the portion about 300 C. or in some cases above 300 C., as the starting point for grease manufacture or lubricating oil manufacture, as described in other copending applications, such as applications, Serial No. 395,941, filed July 13,1920, and Serial No. 423,557, filed November 12, 1920.

The. pressure tar which I employed as one of my materials was obtained from the Sinclair Oil Company. It had passed through their usual cracking operation, which was carried out at about 150 to 200 pounds pressure and under a temperature of about 800 to 825 C. This pressure tar material contained over 5% of arcmatic hydrocarbons and many unsaturated hydrocarbons of the aliphatic cyclic series. The fraction of the oxidized product mixture boiling below either of the above points may, in certain cases, be used as a fuel, without other chemical treatment. This product, because of its oxygenated character, burns more rapidly than ordinary hydrocarbon fractions boiling between the same limits. This fraction or portions of it may be blended to make motor fuels of high thermal value and ready combustibility. The entire oxidized product mixture under 300 -C., may be used in kerosene tractors or all kerosene engines, where its peculiar chemical character makes it a highly efficient fuel; This total mixture fraction is also specially valuable as a fuel for engines of the Diesel or semi-Diesel type, as the easy oxidizability of the fuel makes it possible to produce the development of power at lower pressures in such types of engine.

Or as above indicated, it may be separated by distillation into two fractions, one in the gasoline or motor spirit range and another in the kerosene range. In the latter case, on carrying out one type of cracking or further thermal decomposition of the kerosene fraction, from 62 to of the total liquid charged was recovered, this giving from around 30 to nearly 50% of a fraction distilling below 200 C. The amount of motor spirit fuel obtained in this cracking of the kerosene fraction will, of course, depend considerably upon the type of cracking process employed.

. In all cases, that portion of the oxidation product materially distilling above the kerosene range may be treated for producing industrial products, such as lubricants, greases, etc.

Changes may be made in the form of apparatus employed, the temperatures used, the methods of cracking employed, etc., without departing from my invention.

My parent application Ser. No. 473,798, filed May 31, 1921, now pending, and another of my copending applications, Ser. No. 702,136, filed March 26, 1924, contain broader claims relating to fractioning complex mixtures such as produced by my partial oxidation process, and to a resulting fraction, and to further treating such a fraction. No claim except claim 4 herein is limited to an oxidation process where the reaction zone is maintained at a temperature near 400 C.

I claim:

1. The method of treating petroleum consisting in cracking the same, fractioning the cracked product, and partially oxidizing a fraction of the cracked product.

2. The method of treating petroleum consist-.

ing in cracking the same, fractioning the cracked product, partially oxidizing a fraction of the cracked product, and fractioning the oily oxidized product into fractions of different average molecular weight, each containing oxygen derivatives of hydrocarbons of different molecular weights.

3. The method consisting of partially oxidizing a cracked petroleum fraction, fractioning the oily partially oxidized product, and cracking a fraction of said oxidized product.

4. In the partial oxidation of liquid mainly aliphatic hydrocarbons, the steps consisting of mixing the same with a gas containing free oxygen, passing the same through a reaction zone, maintaining the reaction zone at a temperature near 400 C., and using an air ratio greater than theory demands to supply the proper amount of free oxygen.

5. The method of treating a mineral oil which comprises cracking the oil, fractioning the product, mixing a cracked fraction in finely divided condition with a gas containing free oxygen, passing the same through a hot reaction zone under reactive conditions, and chemically tying oxygen into the cracked mineral oil fraction.

6. The method of treating petroleum consisting in cracking the same, partially oxidizing at least a portion of the cracked product to form an oily oxidized product, and fractioning said oily oxidized product into fractions of different average molecular weights, each containing oxygen derivatives of hydrocarbons of different molecular weights. 1

7. As a composition of matter, a liquid fractionated portion of cracked and oxidized mineral oil in the range from alcohols to organic acids and containing like bodies of different molecular weights.

8. As a new composition of matter, a liquid fractionated portion of a partial oxidation cracked mixture of hydrocarbons of different molecular weights of different degrees of oxidation including alcohols and aldehyde-like bodies of different molecular weights.

' JOSEPH HIDY JAMES. 

